Vat dyes of the anthraquinone-azole series



Pat ented Mar. 4, 1 952 VA-T DES GFTHE AN THRAQUlNON E -AZOEE SERIES Herman..E...Schroede1- Kennett Square, Pa., and Joseph Deinet, Glassboro, N. J., assignors to E. I. du Pont de Nemours &: Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 24; 1950, Serial No. 151,806

6 Claims. (Cl. 260-'7 This invention relates to the preparation of new and valuable vat dyes of the anthraquinone oxazole and thiazole; series, and more particularly to new unsymmetrical azobiphenyl carbonylaminoanthraquinone compounds which contain in the molecule an anthraquinone- 1-,2(N)-oxazole or thiazole group. The compounds of this invention have the general formula:

in which Y stands for one of the elements S and --O, X stands for a member of the group consisting of hydrogen, bromine and ch10,- rine, and R. stands for a vattable anthraquinonyl radical of the group consisting of an unsubstituted anthraquinonyl radical and the anthraquinonyl radicals carrying simple monovalent substituents of the group consisting of -Cl, -Br, methyl, methoxy, methylthiol, and simple acylamino groups such as the benzoylamino. and

thenoylamino groups, said anthraquinonyl radicals being attached to the wCONH-group in the beta. position.

This application is a continuation-impart, of our co-pending application Serial Nos 99,873, filed June 17, 1949., now Patentv No. 2,559,669, issued July 10, 1951.,

The beta-anthraquinonylamide compounds of this invention, as above formulated, are characterized by their exceptional stability when applied to the fiber by hot dyeing methods (e. g. 180 F.). more particularly described in our application Serial No. 99,873, when dyedat 180 R, lose some strength and develop some dullness and reddish shade. Although the products of Serial No. 99,873 are excellent yellow vat dyes when applied by the cold dyeing method, the instant colors may be applied by either the cold or hot dyeing The corresponding alpha-amides,

exhibit good brightness, tinctorial strength and rastnessproperties; It is amore specific object of the invention to produce anthraquinone vat dyes which can be dyed either by cold: or hot dyeing methods, and which carry an anthraquinone aminocarbonyl group linkedthrough the beta position.

These colors are best prepareclin a non-reactive medium by condensing a 4 ,4'-az obiphenyl- 4",4"-dicarbonyl chloride with 2-amino-1-halogen anthraquinone to produce the oxazole or with a 11-mercapto-2-aminoanthraquinone to produce the; thiaz ole at temperatures; in the range of from to, C.,.andthen turthercondensr ing the resulting compound without; isolation with a beta-aminoanthraquinone compound at temperatures in the range of from to,220=0. The diamido compound so obtained is ring-closed to the oxazole or thiazole; in the same solution, wit or witho the dd ti n of acid b n and catalysts, at elevated tem er tu usually n th ange f m. 160 to 20 0- If: des red n zobiphenylcarh y (b ta amin antnr qua ms-car y c o de ma be c nde with a 2am no-h oeen nthra uine or 2- aminoant raquinone-lwrncrcapt N alt and then, ring closed to the corresponding ox az ole or h znl in e s me mann r; r by n n in 4 (1,2(N) anthraquinoneoxazolylj) az obiphenyll -carbonyl chloride with a beta- ,aminoanthraquinone compound.

he p oducts ma b co di i n d r: dy in nih sua mannepsue as y illing, or acid pasting with or without purification by bleaching with sodium hypochlorite customarily employed in purifying vat dyestuffs of the anthraquinor e series. These new vat dyes are bright yellow pastes. They dye cotton and related fibers in strong, bright yellow shades from redbrown alkaline hydrosulfite vats, and the dyeings show very good light-fastness and tinctorial strength. The dyes may be applied by cold or hot dyeing methods. They dye rapidly and exhaust well. l

The en n exampl s ar g ven. t illustrat th n e t n The part used are b weigh aeeaeee Ti 3 4 Example 1 product, upon acid pasting and bleaching with Nine hundred (900) parts of mtrobenzene, 2 sodium hypochlorite, forms a bright yellow paste parts of pyridine, 50 parts of 4,4, azobiphenyl and dyes cotton from a sodium hydrosulfite vat l, acid and 43 parts of thionyl in bright yellow shades of excellent fastness chloride are agitated and heated at 95 to 100 0. 5 pmpertlesj for 18 to 20 hours. The mass is then air blown Example 3 for one-half hour to remove excess of thionyl Six hundred (600) parts of nitrobenzene, 14.1

chloride. 30.5 parts of 1-chlor-2-aminoanthraparts of 2-amino-3-bromoanthraquinone and 30 quinone are added, the reaction mass is heated parts of the following carboxylic acid chloride:

t to 138-140 C., and agitated at this temperature as described in Example of Schroeder 8: Deinet for 6 hours. After cooling to 100 C., 26.5 parts of application Serial No. 99,873, are heated together 2-aminoanthraquinone are added, then the mass to-210 C. and maintained at this temperature is heated to 210 C. and maintained at this temfor 1 /2- hours. The reaction mass is then cooled perature for one hour. After cooling to 100 0., to 50 C., filtered, the filter cake is washed with 50 parts of sodium carbonate, 50 parts of potasnitrobenzene and alcohol in turn, and dried.

S m c 1 P t Of p c acetate and 1 P The product is then acid pasted and bleached of cuprous chloride are added, the mass is then 2 heated to 210 C. and maintained at this temyellow pasteand dyes cotton from a sodium hyperature for 3 hours. The reaction mass is then dr lfite vat, in very bright yellow shades of cooled to 50 C., filtered, the filter cake is washed ex nem; fastness properties.

Z1131 ciiriitaribenzene, alcohol and hot water in turn E m m 8 4 After acid pasting and bleaching with sodium Twelve hundred (1200) parts of nitrobenzene, hypochlorite, the product forms a bright yellow 55*parts of 4,4-azobiphenyl-4",4-dicarboxylic paste and dyes cotton from a sodium hydrosulfite acid chloride and 26.5 parts of 2-aminoanthravat in bright yellow shades of very good fastness quinone are heated together to 140 C. and mainproperties. tained at this temperature for 6 hours. The re- The product of this example has the following action mass is then cooled to 25 C. and parts structural formula: of 1,3-dibromo-2-aminoanthraquinone are added.

wxiwNNwC ONH acid chloride and 30.5 parts of 1-chloro-2-amino- Example 2 I The mass is then heated to 200 C. and mainelve hun ed (1200) parts of trobe 5 i a c ztion miss is theg z lfi 100 h d after 4 r n r!! v o 55 parts of azob1pheny14 dlcarboxyhc addition of parts of sodium carbonate, 50

anthraquinone are heated together to 138-140 Parts pmssium meta, 1 Part cupri" 0C and maintained for 6 mum The reaction tate and 1 part of cuprous chloride, is heated to mass is then cooled to 50 C. and 28.5 parts of and agitated at this temperature for 3 2 amino 3 methy1anthmquinone are added and hours. The mass is then cooled to 50 C., filtered,

the reaction mass is heated to and and the filter cake is washed with nitrobenzene, tated at this temperature for 2 hours. The realcohol and Walter in turn, and driedaction mass is then cooled to 100 C., 50 parts of The produ 15 then d p s a d bl ac ed sodium carbonate, 50 parts of potassium acetate, with Sodium hypbchlorite- It f s a bright ye 1 part of cupric acetate and 1 part of cuprous w p ste and es cotton from a sodium hy rochloride are added, thereafter heated to 210 C., ulf e vat in bri y w Shades of good fastand reacted at this temperature for 3 hours. ness pr p r and has theiormulai The reactionmass is then cooled to C., filtered, V 5 the filter cake is washed with nitrobenzene, al- Twelve hundred (1200) parts of nitrobenzene, 'cohol and hot water in turn, and dried. The 55 parts of 4,4'-azobiphenyl-4",4"'-dicarboxylic with sodium hypochlorite. It forms a bright V acid chloride and 39 parts of 1-bromo-2-amino anthraquinone are heated together to 148 (Land maintained at this temperature for 6 hours. The reaction mass is then cooled to 50 C., and after addition of 26.5 parts of Z-aminoanthraquinone, is heated to 210 C. and agitated at this temperature for 1 hours. The mass is then cooled to 100 C. and 50 parts of sodium carbonate, 50parts of potassium acetate, 1 part of cupric acetate and 1 p Of cuprous chloride are added, thereafter heated to 210 C. and agitated at this temperature for 3 hours. The reaction mass is then cooled to 50 C., filtered, the filter cake is washed with nitrobenzene, alcohol and hot waterin turn, and dried.

The product is then acid pasted andbleached with sodium hypochlorite. It forms a bright yellow paste and is identical with the product of Example 1.

Example 6 added, the whole is then heated to 210 C. and maintained at this temperature for 3 hours. The reaction massis then cooled' to 60 C., filtered, the filter cake is washed with nitrobenzene, alcohol and hot water in turn, and dried.

The product is then acid pasted and bleached with sodium hypochlorite. It forms a bright yellow paste and dyes cotton from a sodium hydrosulfite vat in very bright yellow shades of excellent fastness properties. It has the formula:

Example 7 parts of Z-aminoanthraquinone. and. 46 partslof 4,4'-azobiphenyl-4",4"-dicarboxylic acid chloride are heated together to 138-140 C. and maintained for 6 hours While agitating. The mass is then air blown for /2 hour to remove hydrochloric acid. After cooling to 25 C., 27.7 parts of l-mercapto-(Na salt) 2-aminoanthraquinone are added and. the mass heated to 210 C; and maintained at this temperature! for: 1 /2 hours. The reaction mass is then cooledto 50 C., filtered, the filter cake is washed with: nitrobenzene, alcohol and hot water in turn, and dried.

After acid pasting and bleaching with sodium hypochlorite, the product forms a bright yellow paste and dyes cotton from a sodium hydrosulfite vat in bright yellow shades of very good fastness properties.

This product has the formula:

In place of the amino halogen compounds deiscribed in the examples, we may use 2-amino-1- bromo-3-chloroanthraquinone to produce -the oxazole portion of the. molecule.

In the formation of the amide portion of the molecule, excellent dyestuffs are obtainable by using, one molecular equivalent of 2-amino-1-mercaptoanthraquinone, 2-amino-1-benzo'lyaminoanthraquinone, 2-am ino-l-chl'oroanthraquinone, or 2-amino-l,3- dichloroanthraquinone,.or similar beta-aminoanthraquinone compound.

We claim:

1. The compounds of the formula:

in which Y stands for an element of the group consisting of S- and -O--, X stands for a member of the group consisting of hydrogen, bromine and chlorine, and R stands for a vattable anthraquinonyl radical of the group consisting of an unsubstituted anthraquinonyl radical and the anthraquinonyl radicals carryin monovalent substituentsof the group consisting of -Cl, --Br, methyl, methoxy, methyl-thiol, and benzoylamino radicals ortho to the --CONH- group, said S CH:

anthraquinonyl radicals being attached to the Ten hundred (1000) parts of nitrobenzene, 22.3 --CONH group in the beta position.

2.. The compound of the formula:

SCH:

3. The compound of the formula:

l l B 4. The compound of the formula:

5. The compound of the formula:

(I) lL 6. The compound of the formula:

HERMAN E. SCHROEDER. JOSEPH DEINET.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 848,018 France July 17, 1939 

1. THE COMPOUND OF THE FORMULA: 